Cycloimidine derivatives and process for preparing same



CYCLOIMIDINE DERIVATIVES AND PROCESS FOR PREPARING SAME Hans S.Mannheimer, New York, N. Y.

No Drawing. Application May 21, 1956, Serial No. 585,940

a 12 Claims. (Cl. (H-309.6)

This invention relates to novel-compositions and to methods forproducing them. 'In one of its: more specific aspects the invention isdirected 'to novel derivatives of metal'salts .of; substitutedquaternary hydroxy cycloimidinic acid. metal 'alcoholates, examples ofwhich areare non-vesicant and non-toxic to human and animal life and maybe introduced into the bloodstream without ill effects. cellentsynthetic detergents, softeners and dye assistants in the textile andrelated fields and especially in washing and cleansing of cotton fibersand textiles. They may also be employed as therapeutic agents and areespecially useful in germicides, fungicides and antisepticides.

Said cycloimidates have the following general Formula I:

in which R is the organic radical which if connected to a carboxyl groupprovides a monocarboxylic acid and said radical contains at least 4carbon atoms; R2 isan aliphatic hydrocarbon grouphavingl to 4 carbonatoms, such as -CH2-",C2H4-, CsHs-, and C4Ha or any of the aforesaidgroups, any one or more of these hydrogens may be hydroxy substituted,illustrative examples of which are -CH2CHOHCH2,

or any one of the aforesaid groups either unsubstituted or hydroxysubstituted andhaving a single'ether (O-) or keto (--C-) linkagetherein; illustrative examples of which are C2H4-O'-1-C2H4'- I -CH2CHQI-I O C2H4- -CH2CO--CH2; both M radicals may be the same as or differentfrom each other and each is ametal and preferably an alkali metal andfor most purposes is so.-

dium or potassium.

The methods for producing said cycloumdates and illustrative examples ofa number of specific cycloimidates are disclosed in said patent. h V 7They are surface active agents andserve as ex Prior to this invention,it was known that cationic surface active agents and anionic surfaceactive agents when together in aqueous solution resulted in theproduction or formation of water insoluble compounds; and that adding ananionic surface active agent to an aqueous solution of another anionicsurface active agent resulted in a mere physical combination of saidagents and that no reaction would occur between them.-

Said cycloimidates normally behave anionically' in aqueous solutionshaving a pH above 7, and consequently it was expected that saidcycloirnidates" when in aqueous solution together with anionic surfaceagents that they would be combined physically only and that no otherreaction would occur therebetween. In the course of my experimentations,I have discovered that said cycloimidates could be reacted with certainanionic surface active agents at a pH above 7 to produce water' solublereaction products. I Not only did I make said discovery, but I furtherdiscovered that water solutions of such reaction products hadviscosities greater than corresponding aqueous solutions of thecycloimidates and also exhibited better foaming characteristics than didsaid cycloimidates in very low dilutions under extreme water hardnessconditions. Said reaction products are non-toxic and non-irritating tothe human skin. They have been found eminently useful as general utilitydetergents, such as for car washing, dish Washing, clothes washing,textile softeners, etc.

According to this invention, one or a combination of two or more of saidcycloimidates of the general structural Formula I are reacted with oneor a combination of two or more anionic surface active agents of thefollowing general structural Formula II to provide novel, water-solublecompounds having the following general structural Formula III, andhaving high wetting, de tergency and surface active properties-andcapable of providing voluminous and stable foams in aqueous solutions.Said compounds of Formula I and Formula either alone or in mere.physical combination with each other and employed as components ofshampoos caused stinging and sometimes-irritation of the eye when suchshampoos accidentallyv reached the eyes ofjthe userwhen shampooing ofthe hair. As distinguished therefrom, the novel reaction products ofFormula =H=I when used as componentsof shampoos do not causeeither'st-inging or irritation of the eyes;

FORMULA II FORMULA In ing one or more of the hydrogen atoms thereofsubstituted by one or more hydroxy groups, or said unsubstituted or saidsubstituted hydrocarbon radicals having oneor more ether linkages (--O-)therein; R4 is an organic group selected from the class consisting ofallphatic, aromatic, and aliphatic-aromatic hydrocarbon groups .of 1 12carbon atoms; said hydrocarbon groupsof -l-12 carbon atoms with one ormore of the hydrogen Patented Feb. 12, 1957 atolrtssthereof being.substituted by a. hydroxy group, said.

unsubstituted or substituted hydrocarbon groups having one or more etherlinkages therein; and said aliphatic hydrocarbon? groups". having a*CONHi-linlage: therein;

X: is: S03E01? 0593;. is; analkali metal: or itstequival'enthydrochloric, sulphuric or itsequivalent hasrbeen: added and: preferablysodium or potassium;v and has? heretw fore been defined in, Formula I,as wasiRzL According; to this invention, I react a: compound ofFormulatl with -a compound of FormulatII to provide the novel and highlyuseful compounds of'Formul-a III. In general! this reaction is carriedout in a solution containingcompounds. I and II and: to which a;quantity of' an. acidictagent such as astrongmineralacid, as:for'example. to-lowerthe pHiorthe solution to ava'lue?of'approximately7'to approximately=9 and while maintainin'gtlie mass-at atemperaturebetween approximately 100 -200 F. Inthis reaction under theaforesaid conditions, the quaternar yhydroxy of 'th'e' compound ofFormula I combines with the metalof the compound of Formula II:to-pro'ducethe metal hydroxy and the metal of the OM group of compoundFormula I is replaced by hydrogen due tothe acidic agent addition whichalso at least in partreacts" compound of Formula 11- may beequimolecular for goodyield of compounds of Formula III, I may employ anexcess of either and in general the mole ratio for; componnd of FormulaI to compound of Formula II maybe 2'moles of the former'to 1-3 moles ofthe latter.

One of the'specific methods which I prefer to emplo} in carrying outanaspect of this invention is to first dissolvea compound of Formula Iin water and then thepH thereof is adjusted to approximately 12-13(measured electrically) bythe addition of aqueous caustic soda ifrequired. The temperature of said solution israised to 100 200" F. andpreferably in factory practice to 1 40; F. Then a quantity of a compoundof Formula II is dissolved" in water ina separate container and thissolution is added to said first solution and themass is maintainedinsaid temperature range while being constantlystirred and an acidicagent is addedthereto to reduce the pH thereof to avalue inthe range ofapproximately- 7 to 9; and preferably of approximately 8.2' toapproximately 8.7. At the end of the acidic agent addition, the'stirring is continued and the temperature of the mass maintained forabout 10-20 minutes after which the solution is allowed to cool and is afinished product.

The following are specific examples merely given by way of illustratingthe invention and are not to be taken by way of limitation, all partsbeing given by weight unless otherwise specified.

Example 1 An aqueous solution of 400 parts of the lauric cycloimidatesof Example '1 of iny heretofore identified patent, in 600 parts of wateris heated to approximately 140 F. and its pH adjusted to l2-13 measuredelectrically) and its pH adjusted by the addition of aqueous causticsoda to 12-13. While being constantly stirred and maintained at thattemperature there is added a solution of 400 parts of sodium salt oflauroyl monoethanolamide sulfate: I I t in 600 parts of'wate'r; Thenwhile stirring and temperature is maintained there is added theretobetween about The resultant solution can be used I Stu-4Q parts ofhydrochloric acid solution (32%.) whereby v the pH of the mass islowered to a value in the range'of lauroyl monoethanolarnide sulfate areused.

productiis, arsolutiontof thenovelreaction prcducthaving the followingformula:

Example, 2

Employ the sameprocedure aud componentsas setforth in Example 1. exceptthat only- 200; parts of the In this instance the resultant'product is asolution of the reaction product whose structural formula is shown inExample 1 together withunreactedlauric cycloi midate used, in: the

approximate proportion 052 parts of'the'former to 1 of the latter. a V

Einplo'ythesame procedure as that-set forth; in Example 1,-butemploy thecomponents indicated in the follow ing- Examples 3-l();-the quantity ofhydrochloric acid solution (32%) is variable to lower the pH-to-valuesindicated in- Example 1 to obtain the reaction products of said Examples3-10.

' Example 3" 400. parts-cf lauroyl cycloirnidate (same. as Examplev 1)in 600' parts of water. 400 parts of lauryl taurate. sodium salt;

Example 4 350 parts of caproyl cycloimidate of Example 3 of myhereinbefore identified patent in 650 parts of water.

450 parts of oleyl diethanolamide sulfate sodium salt:

ind-5Q parts of water.

. ronuura' or reaction PRonuc'r CH1 I i N/ Fem CzHt-OH GoHio--(j-1L .0ounce *QHPQOQNZI,

Example 5- I 400 parts of lauroyl cycloimidate (same as Example 1) in600 parts of water. i

in 600 parts of water.

40O' parts of lauroyl triethoxyetheramide'sulfate, sodium FORMULA onREACTION PRODUCT Cn 2a 1 I(OaH40)sS0a y Examp lefi r 400 parts oflauroyl cycloimidate (same as Example 1) in 600 parts of water.

400 parts of lauroyl amidodiethoxyetherethanolmonosulfate sodium salt: a

oumt-i i-llt-olmmrc o out-s pm dissolved in 600 parts of water.

FORMULA 0F REACTION PRODUCT OnH2a O I I- C H4NHCOOH:.SO:

I Example 8 v 450 parts of myristoyl cycloimidate of Example 8 of myhereinbefore identified patent dissolved in 7 00 part s of water.v a

300 parts of lauryl sulfanilamide'sodiu'm salt:

t 0 H V 1 ouna ii l vgs o=Na dissolved in 450 parts of water. A s

FORMULA on nnactt roiv PRODUCT OH: N i om C1H4OH OiaH:r-C-N I CHzCOONa0a a t I? H CuHu-C-AIGS Example 9 140i) parts of laui-oyl cycloimidate(same as Example 1 ir"1 GOOparts of water. Q V

350 parts of lauryl amido methyl methylphenyl sulfonate sodium salt:

oncHa 1 dissolved in 500 parts of water.

FORMULA 0F REACTION PRODUCT t on,

N/ \CH2 7 a I CIHA-OH O11H|sCN 4 r \CHICOONE OiiHn( '!l} T-O -S Oa onon;

Example 10 480 parts of stearoyl cycloimidate in 750 parts of water.

415 parts of stearoyl methyl taurate sodium salt:

O CH:

C l7H3$-( I C2H44 O Na.

in 625 parts ofvwater.

FORMULA 0F REACTION PRODUCT N "om C2H4-(OH Gl7H3PC-.N I

, 0 OH: em -000m I c11Hat-i 1 I clH4-soa The specific cycloimidates,used in Examples 1-10 1 herein may be replaced by any of the otherspecific .cy-

cloimidates of my hereinbefore identified. patent, such as those ofExamples 2, 4, 5, 7, 10-14 therein; and in.

, Examples 4, 7, and 8 may be substituted for the sulfonate' salt 'ofExample 1 to provide a number of additional.

specific reaction products within the definition of For- It is to beunderstood that when either $03 or 0803 is used in the specification orclaims, it is meant to indicate either one or the other because of theirobvious equivalency; it is also to be understood that the use of Na inthe specification and claims is meant to indicate any of the otheralkali metals because of their obvious equivalency; 1

and it'is also to be understood that the CONH linkage when part of R4 inthe specification and claims is meant to indicate either it or NCHObecause of their obvious equivalency. V

It is also to be understood that instead of first adjusting the pH ofthe cycloimidate to 12-13 before the addition of the compound of Formula11, any other method may be employed torobtain the condition whereby thepH of the solution of 'I and H is at least 10 and preferably l0.511before the addition of the acidic agent to lower the pH of the mass toapproximately 7 to approximately 9. For example, I and II may bedissolved togather and this solution may by the addition of caustic.-

and then at lO-200 F. is ready for the addition of the acidic agent tolower its pH to approximately 7 to approximately 9.-- If desired, therequired amount of acidic agent may be added either before or after thesolution at pH of at least 10 is brought to a temperature in the rangeof l00-200 F.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from its scope, it is intended that all mattercontained in the description shall be interpreted as illustrat-ivc andnot in a limiting sense.

It is also to be understood that'the following claims are intended tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which as amatter'of' language might be said to fall therebetween.

This application is a continuation-in-part of my copending U. S.Application 413,721, filed on March 2, 1954.

I claim:

l. A novel compound of the following formula: I

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is anorganic group selected from the class consisting of (a) aliphatichydrocarbon groups of 1-4 carbon atoms, (b) hydroxysubstituted aliphatichydrocarbon groups of 1-4 carbon atoms, (0) aliphatic ether groups, eachof said groups having a single ether linkage therein and otherwise beinghydrocarbon of 2-4 carbon atoms, (oi) aliphatic ether groups, each ofsaid groups havinga single ethertlinkageftherein and otherwise beinghydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic ketogroups each of-said groups'havin'g a single keto, linkage therein andotherwise being hydro carbon of 2-4 carbon atoms, (f) aliphatic ketdgroups, each of said groups having a single keto linkage therein andotherwise being hydrox'y substituted hydrocarbon of 2-4 carbon atoms; R3is selected from thegroup consisting of (g) hydrogen, (h): aliphatichydrocarbon radicals of l-8 carbon atoms, (,i) h'yd'roxy substitutedaliphatie hydrocarbon radicals of l-8 carbon atoms, (j) aliphatic etherradicals, each of said radicalshaving ether linkage therein andotherwise being hydrocarbon of Z-Srcarbon'" atoms, (k) aliphatic etherradicals, each of said radicals) having ether linkage: thereinand-otherwise being'hydroxy substitutedhydrocarbon 0132-8 carbonatomsr'Ri is-an. organic group selected'f'rom the class consisting of,(I).

aliphatic, aromatictand aromatic-aliphatic hydrocarbon groups of 1-12carbon atoms, (in) hydrox'y substituted aliphatic, aromatic, andaromatic-aliphatic, hydrocarbon groups of 1-12 carbon atoms, ()1)aliphatic, aromatic and aromatic-aliphatic groups, each or saidgroupshaving ether linkage therein and othrewisebeing hydrocarbon of2-12 carbon atoms, (0) aliphatic, aromatic and,

aromatic-aliphatic groups having ether vlinkage therein and otherwisebeing hydrox'y substituted hydrocarbon. of

2-12 carbon atoms, (p) aliphatic,.aromatic and aromatic-- each of saidgroups including (CONH) and otherwise being hydroxy substitutedhydrocarbon of 2-12 carbonv atomsaX is a radical, selected from theclass of S03 and 0803; and M is an alkali'metal.

2. A novel compound of the following formula:

n I CIH4-OH 0 III CHr-C O ONa R-i'i-N-OrH -O-S Or 10 in which R is ahydrocarbon radical of 4-18 carbon atoms t t 3. A novel compound of thefollowing formula:

GHI- t i N/ oH, V

I cum-on R-0--N 0 cm CHa-COONB in which R is a hydrocarbon radical of4-18 carbon atoms. 1

4. A novel compound of the following formula:

atoms, 7

5. A novel compound of the following formula:

CH2 N/ \OH: H one RON/ o H om-oooNa R( lIll-(C'2H4Q)I 3 in which R is ahydrocarbon radical of 4-18 carbon atoms.

6. A novel compound of the following formula:

/GEI N o v p H (ta-OH RO-N Qt Ill; cHt-oooua R'-'C-NC2H4NHCO'CH3=SO33 lin which R is amhydrocarbon radical of 41-18 carbon atoms. t

, 7. The method comprising under pH conditions of approximately 7to'approximately 9 reacting with each other compounds of the followingFormulas I and II:

6O FORMULA 1 /OHr N CH2 7 l/ 6a) ER O V N\ a i Rt-cooM OH 76 FORMULA IIt r R-C-'-N-R4-X-M in which R is a hydrocarbon radical of t4-l8 carbon 7atoms; R: is an organic group selected from the class consisting of (a)aliphatic hydrocarbon groups of l-4 carbon atoms, (b) hydroxysubstituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (c)aliphatic ether groups, each of said groups having a single etherlinkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d)aliphatic ether groups, each of said groups having a single etherlinkage therein and otherwise being hydroxy substituted hydrocarbon of2-4 carbon atoms, (e) aliphatic keto groups each of said groups having asingle keto linkage therein and otherwise being hydrocarbon of 2-4carbon atoms, (f) aliphatic keto groups, each of said groups having asingle keto linkage therein and otherwise being hydroxy substitutedhydrocarbon of 2-4 carbon atoms; R3 is selected from the groupconsisting of (g) hydrogen, (h) aliphatic hydrocarbon radicals of 1-8carbon atoms, (1) hydroxy substituted aliphatic hydrocarbon radicals of1-8 carbon atoms, (j) aliphatic ether radicals, each of said radicalshaving ether linkage therein and otherwise being hydrocarbon of 2-8carbon atoms, (k) aliphatic ether radicals, each of said radicals havingether linkage therein and otherwise being hydroXy substitutedhydrocarbon of 2-8 carbon atoms; R4 is an organic group selected fromthe class consisting of (l) aliphatic, aromatic and aromatic-aliphatichydrocarbon groups of 1-12 carbon atoms, (m) hydroxy substitutedaliphatic, aromatic and aromatic-aliphatic hydrocarbon groups of 1-12carbon atoms, (n) aliphatic, aromatic and aromatic-aliphatic groups,each of said groups having ether linkage therein and otherwise beinghydrocarbon of 2-12 carbon atoms, aliphatic, aromatic andaromatic-aliphatic groups having ether linkage therein and otherwisebeing hydroxy substituted hydrocarbon of 2-12 carbon atoms, (p)aliphatic, aromatic and aromaticaliphatic groups, each of said groupsincluding (CONH) and otherwise being hydrocarbon of 2-12 carbon atoms,(q) aliphatic, aromatic and aromatic-aliphatic groups, each of saidgroups including (CONH) and otherwise being hydroxy substitutedhydrocarbon of 2-12 carbon atoms; X is a radical selected from the classof S03 and 0803; and M is an alkali metal.

8. The method comprising to a solution containing a compound of FormulaI and a compound of Formula II both defined in claim 7, adding aquantity of an acidic agent to lower the pH thereof to a value ofapproximately 7 to approximately 9 and maintaining the temperature ofthe mass between about F. and 200 F.

9. The method comprising to a solution whose pH is at least 10 andcontaining a compound of Formula 1 and a compound of Formula II bothdefined in claim 7, adding a quantity of an acidic agent to lower the pHthereof to a value of approximately 7 to approximately 9 and maintainingthe temperature of the mass between about 100 F. and 200 F.

10. The method defined in claim 7, with the mole ratio of compound ofFormula I to compound of Formula II being 2 moles of the former to 1-3moles of the latter.

11. The method defined in claim 8, with the mole ratio of compound ofFormula I to compound of Formula It being 2 moles of the former to l-3moles of the latter.

12. The method defined in claim 9, with the mole ratio of compound ofFormula I to compound of Formula II being 2 moles of the former to l-3moles of the latter.

No references cited.

1. A NOVEL COMPOUND OF THE FOLLOWING FORMULA: